Laundry bleaching processes and compositions

ABSTRACT

PCT No. PCT/US97/15976 Sec. 371 Date Mar. 13, 1999 Sec. 102(e) Date Mar. 13, 1999 PCT Filed Sep. 10, 1997 PCT Pub. No. WO98/11192 PCT Pub. Date Mar. 19, 1998The present invention relates to the bleaching of fabrics with liquid compositions comprising a peroxygen bleach and a solvent system comprising a hydrophilic solvent and a hydrophobic solvent. These compositions deliver improved stain removal on a variety of stains including bleachable stains, greasy stains, enzymatic stains and mud/clay stains.

TECHNICAL FIELD

The present invention relates to the bleaching of fabrics.

BACKGROUND

A great variety of cleaning compositions have been described in the art.A problem associated with common cleaning compositions, when used inlaundry application to treat different kinds of fabrics, includingcotton and synthetic fabrics such as polyesters, polyamides and thelike, is that they do not deliver an effective performancesatisfactorily meeting consumer's needs, on all types of stainsincluding greasy stains, enzymatic stains, mud/clay stains and the like.

It is thus an object of the present invention to provide overallimproved stain removal performance on a wide range of stains whiledelivering excellent bleaching performance.

It has now been found that this object can be met by bleaching fabricswith a liquid composition comprising a peroxygen bleach and a solventsystem comprising a hydrophobic solvent, i.e., a solvent having ahydrophilic index of less than 18, and a hydrophilic solvent, i.e., asolvent having a hydrophilic index of more than 18, wherein thehydrophilic index is defined by the following equation: ##EQU1## Indeed,it has been found that liquid compositions comprising a peroxygen bleachand such a solvent system, when used in a laundry operation, boost theremoval of various types of stains including greasy stains,mud/clay-containing stains, enzymatic stains, as well as bleachablestains.

An advantage of the present invention is that excellent performance isprovided in a variety of laundry applications, e.g., laundry detergent,or laundry additive, and preferably laundry pretreater.

In a preferred embodiment of the present invention the liquidcompositions used herein may also comprise a bleach activator, whichwill react in an aqueous medium with hydrogen peroxide to form thecorresponding peracid. It has been observed that this peracid is moreeffective at lower temperatures, e.g., at those temperatures where thepretreatment operation is usually performed (20° C.-25° C.), and thusallows the compositions herein to deliver more effective bleachingperformance across a wider range of temperatures.

Another advantage of a particular embodiment of the present invention isthat when such a solvent system, as described herein, is added in aliquid bleaching composition of the present invention formulated as anemulsion or a microemulsion, the viscosity of said composition isreduced, whatever the viscosity was before the addition of said solventsystem. Thus, in one embodiment the present invention also providesliquid emulsions or microemulsions comprising a peroxygen bleach and asolvent system, as described herein, wherein the viscosity can beconveniently controlled while maintaining adequate physical stability,without the need to add any viscosity control agent which would raisethe formula cost, and add bulk to the compositions without contributingto the bleaching/cleaning performance of said compositions.

EP-A-126545 discloses liquid scouring cleaners comprising an abrasive,at least 0.1% of terpene (e.g., d-limonene), at least 0.1% of benzylalcohol and optionally surfactants, builders and the like. Thecompositions clean both greasy and particle soils from hard surfaces. Nobleaches are disclosed. No laundry application is disclosed.

EP-A-216416 discloses liquid scouring cleansers (pH 8-12) with paraffinsulfonate and alkyl benzene sulfonate, 0.5%-10% of a mono- orsesquiterpene, 0.5%-3% of a polar solvent, an acrylic polymericthickener, an abrasive and a viscosity enhancing compound. No bleachesare disclosed. No laundry application is disclosed.

EP-A-137616 discloses laundry liquid compositions formulated in the formof an emulsion having a pH of 6.5 or above and comprising at least 5% byweight of solvents. Such solvents include terpene and terpenoid solvents(e.g., pinene, d-limonene) as well as other solvents like benzylalcohol, n-hexanol, paraffins. Mixtures of orange terpenes and benzylalcohol are especially suitable for removing certain types of stainslike dirty motor oil. The addition of non-polar solvents like benzylalcohol, n-hexanol, mixed fatty alcohols, increases the stability.Pretreating of fabrics and through the wash treatment with suchcompositions are disclosed. No bleaches are disclosed.

SUMMARY OF THE INVENTION

The present invention encompasses a process of bleaching a fabric with aliquid composition comprising a peroxygen bleach and a solvent systemcomprising a hydrophilic solvent having a hydrophilic index of more than18, and a hydrophobic solvent having a hydrophilic index of less than18, wherein the hydrophilic index is defined by the equation molecularweight of the hydrophilic part of the solvent ##EQU2## said processcomprising the steps of applying said composition in its neat form ontosaid fabric, preferably only soiled portions thereof, before rinsing, orwashing then rinsing said fabric.

The present invention also encompasses a process of bleaching fabricswhich includes the steps of diluting in an aqueous bath a liquidcomposition in its neat form, comprising a peroxygen bleach and asolvent system as defined hereinabove, contacting said fabrics with saidaqueous bath comprising said liquid composition, and subsequentlyrinsing, or washing then rinsing said fabrics.

Finally, the present invention encompasses a liquid composition suitablefor bleaching fabrics, comprising a peroxygen bleach, and a solventsystem comprising from 0.05% to 20% by weight of the total compositionof a hydrophilic solvent having a hydrophilic index of more than 18, andfrom 0.05% to 10% by weight of the total composition of a hydrophobicsolvent having a hydrophilic index of less than 18, wherein thehydrophilic index is defined by the equation ##EQU3##

DETAILED DESCRIPTION OF THE INVENTION

Processes for Bleaching a Fabric

The present invention encompasses processes of bleaching fabrics,starting from a liquid bleaching composition comprising a peroxygenbleach and a solvent system comprising a hydrophobic solvent and ahydrophilic solvent, as described herein.

Indeed, the present invention is based on the finding that by adding thepresent solvent system, in a liquid composition comprising a peroxygenbleach, improved stain removal performance is obtained with saidcomposition when used to treat a soiled fabric, especially inpretreatment application, as compared to the stain removal performancedelivered with the same composition without said solvent system, orcomprising only one type of solvent, i.e., a hydrophilic solvent or ahydrophobic solvent as described herein, instead of said solvent systemcomprising both a hydrophilic solvent and a hydrophobic solvent.

By "stain removal performance" it is meant herein stain removalperformance on a variety of stains/soils such as greasy/oily stains,and/or enzymatic stains and/or mud/clay stains as well as on bleachablestains.

By "greasy/oily stains" it is meant herein any soil and stain of greasynature that can be found on a fabric like dirty motor oil, mineral oil,make-up, lipstick vegetal oil, spaghetti sauce, mayonnaise and the like.Indeed, the liquid compositions herein have been found to beparticularly effective on make-up and spaghetti sauce.

Examples of enzymatic stains include grass, chocolate and blood.Examples of bleachable stains include tea, coffee, wine and the like.

The stain removal performance of a given composition on a soiled fabric,for example under pretreatment conditions, may be evaluated by thefollowing test method. A composition according to the present inventionis first applied neat on the stained portion of a fabric, left to actthereon from about 1 to about 10 minutes, preferably 5 minutes, afterwhich the pretreated fabric is washed according to common washingconditions with a conventional detergent composition, at a temperatureof from 30° C. to 70° C. for a period of time sufficient to bleach saidfabric. For example, typical soiled fabrics to be used in this stainremoval performance test may be commercially available from EMC(Empirical Manufacturing Company) Cincinnati, Ohio, USA, such as clay,grass, spaghetti sauce, gravy, dirty motor oil, make-up, barbecue sauce,tea, blood on two different substrates: cotton (CW120) and polycotton(PCW28).

The stain removal performance may be evaluated by comparing side by sidethe soiled fabrics pretreated with the composition according to thepresent invention with those pretreated with the reference, e.g. thesame composition without such a solvent system according to the presentinvention. A visual grading scale may be used to assign differences inpanel score units (psu), in a range from 0 to 4.

The processes of bleaching fabrics of the present invention include thesteps of contacting fabrics with a liquid bleaching compositioncomprising a peroxygen bleach and a solvent system, as described herein,neat or diluted, and subsequently rinsing said fabrics. In the preferredembodiment, when the fabrics are "pretreated", the composition isapplied neat on the fabrics, and the fabrics are subsequently rinsed, orwashed and then rinsed in a normal wash cycle. We have observed that thestain removal performance improvement is particularly noticeable withthe compositions used herein when contacted directly with the soiledportion of fabrics, before they are washed/rinsed.

As a first essential element, the liquid compositions used according tothe present invention comprise a peroxygen bleach or mixtures thereof.Such peroxygen bleaches include hydrogen peroxide, or a water solublesource thereof, or mixtures thereof. Indeed, the presence of a peroxygenbleach, preferably hydrogen peroxide and/or hydroperoxide and/oraliphatic diacyl peroxide, contributes to the excellent cleaning andbleaching benefits of the compositions of the present invention. As usedherein a hydrogen peroxide source refers to any compound which producesperhydroxyl ions when said compound is in contact with water.

Suitable water-soluble sources of hydrogen peroxide for use hereininclude percarbonates, persilicate, persulphate such as monopersulfate,perborates, peroxyacids such as diperoxydodecandioic acid (DPDA),magnesium perphtalic acid, perbenzoic and alkylperbenzoic acids, alkylhydroperoxides, peroxides, aliphatic diacyl peroxides and mixturesthereof. Hydrogen peroxide and/or alkyl hydroperoxides and/or aliphaticdiacyl peroxides are preferred to be used in the compositions accordingto the present invention.

Suitable hydroperoxides for use herein are tert-butyl hydroperoxide,cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide,di-isopropylbenzene-monohydroperoxide, tert-amyl hydroperoxide and2,5-dimethyl-hexane-2,5-dihydroperoxide. Such hydroperoxides have theadvantage to be particularly safe to fabrics and color while deliveringexcellent bleaching performance.

Suitable aliphatic diacyi peroxides for use herein are dilauroylperoxide, didecanoyl peroxide, dimyristoyl peroxide or mixtures thereof.Such aliphatic diacyl peroxides have the advantage to be particularlysafe to fabrics and color while delivering excellent bleachingperformance.

Typically, the compositions herein comprise from 0.01% to 20% by weightof the total composition of a peroxygen bleach, or mixtures thereof,preferably from 1% to 10%, and more preferably from 4% to 7%.

As a second essential element, the liquid compositions used according tothe present invention comprise a solvent system comprising a hydrophobicsolvent and a hydrophilic solvent.

By "solvent" it is meant herein any hydrocarbon including aliphaticsaturated or unsaturated hydrocarbons or aromatic hydrocarbons thatcontain or not, one or more alcoholic groups, one or more ether groupsand/or one or more ketone groups.

To define the hydrophilic or hydrophobic character of a solvent herein,the following hydrophilic index (HI) is used: ##EQU4## By "hydrophilicpart" of a given solvent it is meant herein all the groups O, CO, OH, ofa given solvent.

By "molecular weight of the hydrophilic part of a solvent" it is meantherein the total molecular weight of all the hydrophilic parts of agiven solvent.

The hydrophilic solvents to be used herein have a hydrophilic index ofmore than 18, preferably more than 25, and more preferably more than 30,and the hydrophobic solvents to the used herein have a hydrophilic indexof less than 18, preferably less than 17 and more preferably 16 or less.

The combination of these solvents provides improved overall stainremoval performance when added in a liquid peroxygen bleach-containingcomposition on various type of stains like greasy stains (e.g. dirtymotor oil), enzymatic stains (e.g. blood) and clay stains. Furthermore,this solvent system when added in a liquid peroxygen bleach-containingcomposition, further provides improved bleaching efficacy. It isspeculated that said solvents can be a vehicle to the other activeingredients present in said liquid compositions, helping them topenetrate the stains. Indeed, the hydrophobic solvent can be a vehiclefor hydrophobic active ingredients like hydrophobic bleaches (e.g.,dilauroyl peroxide), while the hydrophilic solvent can be a vehicle forhydrophilic bleaches like hydrogen peroxide.

Suitable hydrophobic solvents to be used herein include paraffins,terpenes or terpene derivatives, as well as alkoxylated aliphatic oraromatic alcohols, aliphatic or aromatic alcohols, glycols oralkoxylated glycols, and mixtures thereof, all these solvents have ahydrophilic index of less than 18.

Suitable terpenes (hydrophilic index of O) are mono-and bicyclicmonoterpenes, especially those of the hydrocarbon class, which includethe terpinenes, terpinolenes, limonenes and pinenes and mixturesthereof.

Highly preferred materials of this type are d-limonene, dipentene,alpha-pinene and/or beta-pinene. For example, pinene is commerciallyavailable form SCM Glidco (Jacksonville) under the name Alpha PineneP&F®.

Terpene derivatives such as alcohols, aldehydes, esters, and ketoneswhich have a hydrophilic index of less than 18 can also be used herein.Such materials are commercially available as, for example, the α and βisomers of terpineol and linalool.

All type of paraffins (hydrophilic index of O) can be used herein, bothlinear and not, containing from 2 to 20 carbons, preferably from 4 to10, more preferably from 6 to 8. Preferred herein is octane. Octane iscommercially available for example from BASF.

Suitable hydrophobic alkoxylated aliphatic or aromatic alcohols to beused herein are according to the formula R (A)_(n) --OH wherein R is alinear or branched saturated or unsaturated alkyl group, or alkylsubstituted or non-alkyl substituted aryl group of from 1 to 20 carbonatoms, preferably from 2 to 15 and more preferably from 2 to 10, whereinA is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n isan integer of from 1 to 5, preferably 1 to 2. Suitable hydrophobicalkoxylated alcohol to be used herein is 1-methoxy-11-dodecanol (HI=15).

Suitable hydrophobic aliphatic or aromatic alcohols to be used hereinare according to the formula R--OH wherein R is a linear or branchedsaturated or unsaturated alkyl group, or alkyl substituted or non-alkylsubstituted aryl group of from 1 to 20 carbon atoms, preferably from 2to 15 and more preferably from 2 to 10. Suitable aliphatic alcohols tobe used herein include linear alcohols like decanol (HI=7). Suitablearomatic alcohol to be used herein is benzyl alcohol (HI=16).

Suitable hydrophobic glycols to be used herein are according to theformula HO--CR1R2--OH wherein R1 and R2 are independently H or a C2-C10saturated or unsaturated aliphatic hydrocarbon chain and/or cylic.Suitable glycol to be used herein is dodecaneglycol (HI=16).

Suitable hydrophobic alkoxylated glycols to be used herein are accordingto the formula R--(A)n--R1--OH wherein R is H, OH, a linear saturated orunsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15and more preferably from 2 to 10, wherein R1 is H or a linear saturatedor unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to15 and more preferably from 2 to 10, and A is an alkoxy group preferablyethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.Suitable alkoxylated glycol to be used herein is methoxy octadecanol(HI=11).

Particularly preferred hydrophobic solvents to be used herein included-limonene, dipentene, alpha-pinene, beta-pinene, octane, benzylalcohol, or mixtures thereof.

Suitable hydrophilic solvents to be used herein include alkoxylatedaliphatic or aromatic alcohols, aliphatic or aromatic alcohols, glycolsor alkoxylated glycols, and mixtures thereof, all these solvents havinga hydrophilic index of more than 18.

Suitable hydrophilic alkoxylated aliphatic or aromatic alcohols to beused herein are according to the formula R (A)_(n) --OH wherein R is alinear or branched saturated or unsaturated alkyl group, or alkylsubstituted or non-alkyl substituted aryl group of from 1 to 20 carbonatoms, preferably from 2 to 15 and more preferably from 2 to 10, whereinA is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n isan integer of from 1 to 5, preferably 1 to 2. Particularly suitablealkoxylated alcohols to be used herein include methoxy propanol (HI=37),ethoxy propanol (HI=32), propoxy propanol (HI=28) and/or buthoxypropanol (HI=27).

Suitable hydrophilic aliphatic or aromatic alcohols to be used hereinare according to the formula R--OH wherein R is a linear or branchedsaturated or unsaturated alkyl group, or alkyl substituted or non-alkylsubstituted aryl group of from 1 to 20 carbon atoms, preferably from 2to 15 and more preferably from 2 to 10. Particularly suitable aliphaticalcohols to be used herein include linear alcohols like ethanol (HI=37)and/or propanol (HI=28).

Suitable hydrophilic glycols to be used herein are according to theformula HO--CR1R2--OH wherein R1 and R2 are independently H or a C2-C10saturated or unsaturated aliphatic hydrocarbon chain and/or cylic.Particularly suitable glycol to be used herein is propanediol (HI=45).

Suitable hydrophilic alkoxylated glycols to be used herein are accordingto the formula R--(A)n--R1--OH wherein R is H, OH, a linear saturated orunsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2to 15 and more preferably from 2 to 10, wherein R1 is H or a linearsaturated or unsaturated alkyl group of from 1 to 20 carbon atoms,preferably from 2 to 15 and more preferably from 2 to 10, and A is analkoxy group preferably ethoxy, methoxy, and/or propoxy and n is from 1to 5, preferably 1 to 2. Particularly suitable alkoxylated glycols to beused herein is ethoxyethoxyethanol (HI=37).

Typically, the compositions to used herein comprise from 0.05% to 10% byweight of the total composition of said hydrophobic solvent or mixturesthereof, preferably from 0.1% to 5% and more preferably from 0.2% to 2%,and from 0.05% to 20% by weight of the total composition of saidhydrophilic solvent or mixtures thereof, preferably from 0.5% to 15% andmore preferably from 1% to 10%. Indeed, best overall stain removalperformance has been obtained on different stains including bleachablestains, greasy stains, mud/clay stains and enzymatic-type stains, whensaid solvents are present in a weight ratio of said hydrophobic solventto said hydrophilic solvent of from 1:20 to 1:1, more preferably from1:14 to 1:2.

The compositions to be used according to the present invention must beliquids. As used herein, "liquid" includes "pasty" compositions, andliquid compositions herein preferably have a viscosity of from 1 cps to10000 cps, preferably from 100 cps to 1000 cps, more preferably from 200cps to 600 cps, at 50 rpm shear rate and at 20° C. temperature.

Preferably, the compositions to be used herein are aqueous. Said aqueouscompositions have a pH as is of from 1 to 12, preferably from 2 to 6,and more preferably from 3 to 5, where optimum chemical stability isachieved. The pH of the compositions can be adjusted for instance byusing organic or inorganic acids, or alkalinizing agents.

The compositions used in the present invention may further compriseoptional ingredients like surfactants including nonionic, anionic,cationic, zwitterionic and/or amphotheric surfactants, builders,stabilizers, chelants, soil suspending polyamine polymers, polymericsoil release agents, dye transfer agents, radical scavengers, solvents,brighteners, catalysts, foam suppresors, bleach activators, perfumes anddyes.

In the present invention, the liquid bleaching composition comprising aperoxygen bleach and said solvent system needs to be contacted with thefabrics to be bleached. This can be done either in a so-called"pretreatment mode", where the composition is applied neat onto saidfabrics before the fabrics are rinsed, or washed then rinsed, or in a"soaking mode" where the liquid composition is first diluted in anaqueous bath and the fabrics are immersed and soaked in the bath, beforethey are rinsed, or in a "through the wash mode", where the liquidcomposition is added on top of a wash liquor formed by dissolution ordispersion of a typical laundry detergent. As discussed earlier, thecomposition to perform the processes herein is in the form of a liquidas opposed to a solid or a gas.

It is also essential in these processes according to the presentinvention, that the fabrics be rinsed after they have been contactedwith said composition, before said composition has completely dried off.In the pretreatment mode, it has been found that water evaporationcontributes to increase the concentration of free radicals onto thesurface of the fabrics and, consequently, the rate of chain reaction.Indeed, free radicals typically result from the decomposition ofperoxygen bleach that may be catalyzed due to the presence of metal ionson the surface of a fabric and/or to the exposure of the fabrics to UVradiation from sunlight. It is also speculated that an auto-oxidationreaction occurs upon evaporation of water when liquid peroxygen-bleachcontaining compositions are left to dry onto the fabrics. Said reactionof auto-oxidation generates peroxy-radicals which may contribute to thedegradation of cellulose. Thus, not leaving the liquid compositions, asdescribed herein, to dry onto the fabric, in a process of pretreatingsoiled fabrics, contributes to reduce the tensile strength loss whenpretreating fabrics with liquid peroxygen bleach-containingcompositions.

In the pretreatment mode, the process comprises the steps of applyingsaid liquid composition in its neat form onto said fabrics, or at leastsoiled portions thereof (i.e., directly applying said liquid compositionas described herein onto said fabrics without undergoing any dilution),and subsequently rinsing, or washing then rinsing said fabrics. In thismode, the neat compositions can optionally be left to act onto saidfabrics for a period of time ranging from 1 min. to 1 hour, preferablyfrom 1 minute to 30 minutes, before the fabrics are rinsed, or washedthen rinsed, provided that the composition is not left to dry onto saidfabrics. For particularly though stains, it may be appropriate tofurther rub or brush said fabrics by means of a sponge or a brush, or byrubbing two pieces of fabrics against each other.

In another mode, generally referred to as "soaking", the processcomprises the steps of diluting said liquid-composition in its neat formin an aqueous bath so as to form a diluted composition. The dilutionlevel of said liquid composition in an aqueous bath is typically up to1:85, preferably up to 1:50 and more preferably about 1:25(composition:water). The fabrics are then contacted with the aqueousbath comprising the liquid composition, and the fabrics are finallyrinsed, or washed then rinsed. Preferably in that embodiment, thefabrics are immersed in the aqueous bath comprising the liquidcomposition, and also preferably, the fabrics are left to soak thereinfor a period of time ranging from 30 minutes to 48 hours, preferablyfrom 1 hour to 24 hours.

In yet another mode which can be considered as a sub-embodiment of"soaking", generally referred to as "bleaching through the wash", theliquid composition is used as a so-called laundry additive. And in thatembodiment the aqueous bath is formed by dissolving or dispersing aconventional laundry detergent in water. The liquid composition in itsneat form is contacted with the aqueous bath, and the fabrics are thencontacted with the aqueous bath containing the liquid composition.Finally, the fabrics are rinsed.

Liquid Compositions

The present invention also encompasses a liquid composition suitable forbleaching fabrics, comprising a peroxygen bleach, and a solvent systemcomprising from 0.05% to 20% by weight of the total composition of ahydrophilic solvent having a hydrophilic index of more than 18, and from0.05% to 10% by weight of the total composition of a hydrophobic solventhaving a hydrophilic index of less than 18, wherein the hydrophilicindex is defined by the equation ##EQU5## Said peroxygen bleach andsolvent system are as described hereinbefore.

The liquid compositions of the present invention preferably furthercomprise a surfactant or mixtures thereof. Any surfactant known to thoseskilled in the art may be suitable herein including nonionic, anionic,cationic, zwitterionic, and/or amphoteric surfactants up to 50% byweight of the total composition. Surfactants allow to further improvethe stain removal properties of the compositions according to thepresent invention.

Nonionic surfactants are highly preferred herein for performancereasons. The liquid compositions herein may comprise up to 50% of anonionic surfactant or mixtures thereof, preferably from 0.3% to 30% andmore preferably from 0.4% to 25%. Suitable nonionic surfactants to beused herein are fatty alcohol ethoxylates and/or propoxylates which arecommercially available with a variety of fatty alcohol chain lengths anda variety of ethoxylation degrees. Indeed, the HLB values of suchalkoxylated nonionic surfactants depend essentially on the chain lengthof the fatty alcohol, the nature of the alkoxylation and the degree ofalkoxylation. Surfactant catalogues are available which list a number ofsurfactants, including nonionics, together with their respective HLBvalues.

Suitable chemical processes for preparing the nonionic surfactants foruse herein include condensation of corresponding alcohols with alkyleneoxide, in the desired proportions. Such processes are well-known to theman skilled in the art and have been extensively described in the art.As an alternative, a great variety of alkoxylated alcohols suitable foruse herein is commercially available from various suppliers.

Particularly suitable to be used herein as nonionic surfactants arehydrophobic nonionic surfactants having an HLB (hydrophilic-lipophilicbalance) below 16, preferably below 15, more preferably below 12, andmost preferably below 10. Those hydrophobic nonionic surfactants havebeen found to provide good grease cutting properties.

Preferred hydrophobic nonionic surfactants to be used in thecompositions according to the present invention are surfactants havingan HLB below 16 and being according to the formula RO--(C₂ H₄ O)_(n) (C₃H₆ O)_(m) H, wherein R is a C₆ to C₂₂ alkyl chain or a C₆ to C₂₈ alkylbenzene chain, and wherein n+m is from 0 to 20 and n is from 0 to 15 andm is from 0 to 20, preferably n+m is from 1 to 15 and, n and m are from0.5 to 15, more preferably n+m is from 1 to 10 and, n and m are from 0to 10. The preferred R chains for use herein are the C₈ to C₂₂ alkylchains. Accordingly, suitable hydrophobic nonionic surfactants for useherein are Dobanol^(R) 91-2.5 (HLB=8.1; R is a mixture of C9 and C₁₁alkyl chains, n is 2.5 and m is 0), or Lutensol^(R) TO3 (HLB=8; R is aC₁₃ alkyl chains, n is 3 and m is 0), or Lutensol^(R) AO3 (HLB=8; R is amixture of C₁₃ and C₁₅ alkyl chains, n is 3 and m is 0), or Tergitol^(R)25L3 (HLB=7.7; R is in the range of C₁₂ to C₁₅ alkyl chain length, n is3 and m is 0), or Dobanol^(R) 23-3 (HLB=8.1; R is a mixture of C₁₂ andC₁₃ alkyl chains, n is 3 and m is 0), or Dobanol^(R) 23-2 (HLB=6.2; R isa mixture of C₁₂ and C₁₃ alkyl chains, n is 2 and m is 0), orDobanol^(R) 45-7 (HLB=11.6; R is a mixture of C₁₄ and C₁₅ alkyl chains,n is 7 and m is 0) Dobanol^(R) 23-6.5 (HLB=11.9; R is a mixture of C₁₂and C₁₃ alkyl chains, n is 6.5 and m is 0), or Dobanol^(R) 25-7 (HLB=12;R is a mixture of C₁₂ and C₁₅ alkyl chains, n is 7 and m is 0), orDobanol^(R) 91-5 (HLB=11.6; R is a mixture of C₉ and C₁₁ alkyl chains, nis 5 and m is 0), or Dobanol^(R) 91-6 (HLB=12.5; R is a mixture of C₉and C₁₁ alkyl chains, n is 6 and m is 0), or Dobanol^(R) 91-8 (HLB=13.7;R is a mixture of C₉ and C₁₁ alkyl chains, n is 8 and m is 0),Dobanol^(R) 91-10 (HLB=14.2; R is a mixture of C₉ to C₁₁ alkyl chains, nis 10 and m is 0), or mixtures thereof. Preferred herein are Dobanol^(R)91-2.5, or Lutensol^(R) TO3, or Lutensol^(R) AO3, or Tergitol^(R) 25L3,or Dobanol^(R) 23-3, or Dobanol^(R) 23-2, or mixtures thereof. TheseDobanol^(R) surfactants are commercially available from SHELL. TheseLutensol^(R) surfactants are commercially available from BASF and theseTergitol^(R) surfactants are commercially available from UNION CARBIDE.

Other suitable nonionic surfactants for use herein include polyhydroxyfatty acid amide surfactants, or mixtures thereof, according to theformula

    R.sup.2 --C(O)--N(R.sup.1)--Z,

wherein R¹ is H, or C₁ -C₄ alkyl, C₁ -C₄ hydrocarbyl, 2-hydroxy ethyl,2-hydroxy propyl or a mixture thereof, R² is C₅ -C₃₁ hydrocarbyl, and Zis a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with atleast 3 hydroxyls directly connected to the chain, or an alkoxylatedderivative thereof.

Preferably, R¹ is C₁ -C₄ alkyl, more preferably C₁ or C₂ alkyl and mostpreferably methyl, R² is a straight chain C₇ -C₁₉ alkyl or alkenyl,preferably a straight chain C₉ -C₁₈ alkyl or alkenyl, more preferably astraight chain C₁₁ -C₁₈ alkyl or alkenyl, and most preferably a straightchain C₁₁ -C₁₄ alkyl or alkenyl, or mixtures thereof. Z preferably willbe derived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl. Suitable reducing sugars include glucose,fructose, maltose, lactose, galactose, mannose and xylose. As rawmaterials, high dextrose corn syrup, high fructose corn syrup, and highmaltose corn syrup can be utilised as well as the individual sugarslisted above. These corn syrups may yield a mix of sugar components forZ. It should be understood that it is by no means intended to excludeother suitable raw materials. Z preferably will be selected from thegroup consisting of --CH₂ --(CHOH)_(n) --CH₂ OH, --CH(CH₂OH)--(CHOH)_(n-1) --CH₂ OH, --CH₂ --(CHOH)₂ --(CHOR')(CHOH)--CH₂ OH,where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic oraliphatic monosaccharide, and alkoxylated derivatives thereof. Mostpreferred are glycityls wherein n is 4, particularly CH₂ --(CHOH)₄ --CH₂OH.

In formula R² --C(O)--N(R¹)--Z, R¹ can be, for example, N-methyl,N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, orN-2-hydroxy propyl. R² --C(O)--N< can be, for example, cocamide,stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide,tallowamide and the like. Z can be 1-deoxyglucityl, 2-deoxyfructityl,1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,1-deoxymaltotriotityl and the like.

Suitable polyhydroxy fatty acid amide surfactants to be used herein maybe commercially available under the trade name HOE® from Hoechst.

Methods for making polyhydroxy fatty acid amide surfactants are known inthe art. In general, they can be made by reacting an alkyl amine with areducing sugar in a reductive amination reaction to form a correspondingN-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyaminewith a fatty aliphatic ester or triglyceride in a condensation/amidationstep to form the N-alkyl, N-polyhydroxy fatty acid amide product.Processes for making compositions containing polyhydroxy fatty acidamides are disclosed for example in GB patent specification 809,060,published Feb. 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Pat. No.2,965,576, issued Dec. 20, 1960 to E. R. Wilson, U.S. Pat. No.2,703,798, Anthony M. Schwartz, issued Mar. 8, 1955, U.S. Pat. No.1,985,424, issued Dec. 25, 1934 to Piggott and WO92/06070, each of whichis incorporated herein by reference.

The liquid compositions according to the present invention may furthercomprise other surfactants like an anionic surfactant, or mixturesthereof on top of nonionic surfactants. Anionic surfactants arepreferred herein as optional ingredient as they act as wetting agent,i.e., in a laundry application they wet the stains on the fabrics,especially on hydrophilic fabrics, and thus help the peroxygen bleachperform its bleaching action thereby contributing to improved laundryperformance on bleachable stains. Furthermore, anionic surfactants allowto obtain clear compositions even when said compositions comprisehydrophobic ingredients such as hydrophobic surfactants. Thecompositions herein may comprise from 0.1% to 20% by weight of the totalcomposition of said anionic surfactant, or mixtures thereof, preferablyfrom 0.2% to 15% and more preferably from 0.5% to 13%.

Particularly suitable for use herein are sulfonate and sulfatesurfactants. The like anionic surfactants are well-known in the art andhave found wide application in commercial detergents. These anionicsurfactants include the C8-C22 alkyl benzene sulfonates (LAS), theC8-C22 alkyl sulfates (AS), unsaturated sulfates such as oleyl sulfate,the C10-C18 alkyl alkoxy sulfates (AES) and the C10-C18 alkyl alkoxycarboxylates. The neutralising cation for the anionic syntheticsulfonates and/or sulfates is represented by conventional cations whichare widely used in detergent technology such as sodium, potassium oralkanolammonium. Preferred herein are the alkyl sulphate, especiallycoconut alkyl sulphate having from 6 to 18 carbon atoms in the alkylchain, preferably from 8 to 15, or mixtures thereof.

Other anionic surfactants useful for detersive purposes can also be usedherein. These can include salts (including, for example, sodium,potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of soap, C₈ -C₂₂ primary or secondaryalkanesulfonates, C₈ -C₂₄ olefinsulfonates, sulfonated polycarboxylicacids prepared by sulfonation of the pyrolyzed product of alkaline earthmetal citrates, e.g., as described in British patent specification No.1,082,179, C₈ -C₂₄ alkylpolyglycolethersulfates (containing up to 10moles of ethylene oxide); alkyl ester sulfonates such as C₁₄₋₁₆ methylester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, paraffinsulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,monoesters of sulfosuccinate (especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters of sulfosuccinate (especially saturated andunsaturated C₆ -C₁₄ diesters), sulfates of alkylpolysaccharides such asthe sulfates of alkylpolyglucoside (the nonionic nonsulfated compoundsbeing described below). Resin acids and hydrogenated resin acids arealso suitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tall oil. Furtherexamples are given in "Surface Active Agents and Detergents" (Vol. I andII by Schwartz, Perry and Berch). A variety of such surfactants are alsogenerally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 toLaughlin, et al. at Column 23, line 58 through Column 29, line 23(herein incorporated by reference).

Other suitable anionic surfactants to be used herein also include acylsarcosinate or mixtures thereof, in its acid and/or salt form,preferably long chain acyl sarcosinates having the following formula:##STR1## wherein M is hydrogen or a cationic moiety and wherein R is analkyl group of from 11 to 15 carbon atoms, preferably of from 11 to 13carbon atoms. Preferred M are hydrogen and alkali metal salts,especially sodium and potassium. Said acyl sarcosinate surfactants arederived from natural fatty acids and the amino-acid sarcosine (N-methylglycine). They are suitable to be used as aqueous solution of their saltor in their acidic form as powder. Being derivatives of natural fattyacids, said acyl sarcosinates are rapidly and completely biodegradableand have good skin compatibility.

Accordingly, particularly preferred long chain acyl sarcosinates to beused herein include C₁₂ acyl sarcosinate (i.e. an acyl sarcosinateaccording to the above formula wherein M is hydrogen and R is an alkylgroup of 11 carbon atoms) and C₁₄ acyl sarcosinate (i.e. an acylsarcosinate according to the above formula wherein M is hydrogen and Ris an alkyl group of 13 carbon atoms). C₁₂ acyl sarcosinate iscommercially available, for example, as Hamposyl L-30® supplied byHampshire. C₁₄ acyl sarcosinate is commercially available, for example,as Hamposyl M-30® supplied by Hampshire.

The liquid compositions according to the present invention may furthercomprise other surfactants known to those skilled in the art like anamine oxide surfactant according to the formula R1R2R3NO, wherein eachof R1, R2 and R3 is independently a C₁ -C₃₀, preferably a C₁ -C₂₀, mostpreferably a C₁ -C₁₆ hydrocarbon chain. Amine oxides may be present inamounts up to 10% by weight of the total composition, more preferablyfrom 1% to 3%.

The compositions according to the present invention may further compriseother optional ingredients like builders, stabilizers, chelants, dyetransfer agents, radical scavengers, solvents, brighteners, foamsuppresors, bleach activators, perfumes, soil suspending polyaminepolymers, polymeric soil release agents, catalysts and dyes.

Thus, as an optional but highly preferred ingredient, the compositionsaccording to the present invention comprise a bleach activator ormixtures thereof. By "bleach activator", it is meant herein a compoundwhich reacts with hydrogen peroxide to form a peracid. The peracid thusformed constitutes the activated bleach. Particularly suitable bleachactivators to be used herein are hydrophobic bleach activators, i.e., ableach activator which is not substantially and stably miscible withwater. Typically, such hydrophobic bleach activators have a secondaryHLB (hydrophilic lipophilic balance) below 11, preferably below 10.Secondary HLB is known to those skilled in the art and is defined forexample in "Emulsions theory and practice" by P. Becher, Reinhold, N.Y.,1957, or in "Emulsion science" by P. Sherman, Academic Press, London,1969.

Suitable bleach activators to be used herein include those belonging tothe class of esters, amides, imides, or anhydrides. Examples of suitablecompounds of this type are disclosed in British Patent GB 1 586 769 andGB 2 143 231 and a method for their formation into a prilled form isdescribed in European Published Patent Application EP-A-62 523. Suitableexamples of such compounds to be used herein are tetracetyl ethylenediamine (TAED), sodium 3,5,5 trimethyl hexanoyloxybenzene sulphonate,diperoxy dodecanoic acid as described for instance in U.S. Pat. No.4,818,425 and nonylamide of peroxyadipic acid as described for instancein U.S. Pat. No. 4,259,201 and n-nonanoyloxybenzenesulphonate (NOBS).Also suitable are N-acyl caprolactams selected from the group consistingof substituted or unsubstituted benzoyl caprolactam, octanoylcaprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoylcaprolactam, undecenoyl caprolactam, formyl caprolactam, acetylcaprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoylcaprolactam or mixtures thereof. A particular family of bleachactivators of interest was disclosed in EP 624 154, and particularlypreferred in that family is acetyl triethyl citrate (ATC). Acetyltriethyl citrate has the advantage that it is environmentalfriendly asit eventually degrades into citric acid and alcohol. Furthermore, acetyltriethyl citrate has a good hydrolytical stability in the product uponstorage and it is an efficient bleach activator. Finally, it providesgood building capacity to the composition.

The compositions according to the present invention may comprise from0.1% to 20% by weight of the total composition of said bleach activator,or mixtures thereof, preferably from 1% to 10%, and more preferably from2% to 7%.

The compositions herein may be formulated as solutions, emulsions ormicroemulsions depending on the respective optional ingredients presentand respective levels thereof. For example, for stability reasons, thecompositions according to the present invention that typically comprisea bleach activator, as described hereinbefore, are preferably formulatedeither as aqueous emulsions of said bleach activator in a matrixcomprising water, the peroxygen bleach, the solvent system and anemulsifying surfactant system, or as microemulsions of said bleachactivator in a matrix comprising water, the peroxygen bleach, thesolvent system and a hydrophilic surfactant system.

Preferred peroxygen bleach-containing emulsions herein comprise anemulsifying surfactant system of at least two different surfactants.Preferred herein, said two different surfactants should have differentHLB values (hydrophilic/lipophilic balance) in order to form stableemulsions, and preferably the difference in value of the HLBs of saidtwo surfactants is at least 1, preferably at least 2. Indeed, byappropriately combining at least two of said surfactants with differentHLBs in water, emulsions will be formed which do not substantiallyseparate into distinct layers, upon standing for at least two weeks at40° C.

The emulsions according to the present invention may further compriseother surfactants on top of said emulsifying surfactant system, whichshould however not significantly alter the weighted average HLB value ofthe overall emulsion.

In a particularly preferred embodiment of the emulsions of the presentinvention, wherein the emulsions comprise acetyl triethyl citrate as thebleach activator, an adequate surfactant system, would comprise ahydrophobic nonionic surfactant with for instance an HLB of 6, such as aDobanol^(R) 23-2 and a hydrophilic nonionic surfactant with for instancean

HLB of 15, such as a Dobanol^(R) 91-10. Other suitable nonionicsurfactant systems comprise for example a Dobanol^(R) 23-6.5 (HLB about12) and a Dobanol^(R) 23 (HLB below 6) or a Dobanol^(R) 45-7 (HLB=11.6)and a Dobanol 23-3 (HLB=8.1).

In the embodiment of the present invention where the compositions areformulated as emulsions said compositions are opaque. In centrifugationexamination, it was observed that said emulsions herein showed no phaseseparation after 15 minutes at 6000 rpm. Under microscopic examination,said emulsions appeared as a dispersion of droplets in a matrix.

In the embodiment of the present invention where the compositions of thepresent invention are formulated as microemulsions, said bleachingmicroemulsions according to the present invention comprise a hydrophilicsurfactant system comprising at least two different surfactants like anonionic surfactant and an anionic surfactant. Suitable hydrophilicsurfactants to be used herein are those hydrophilic surfactantsmentioned herein. In the embodiment wherein the microemulsions hereincomprise a peroxygen bleach and a bleach activator, a key factor inorder to stably incorporate the bleach activator in said microemulsionsis that at least one of said surfactants of the hydrophilic surfactantsystem must have a different HLB value to that of the bleach activator.Indeed, if all said surfactants had the same HLB value as that of theactivator, a continuous single phase might be formed, thus lowering thechemical stability of the bleach/bleach activator system. Preferably, atleast one of said surfactants has an HLB value which differs by at least1.0 HLB unit, preferably 2.0 to that of said bleach activator.

In the embodiment of the present invention where the compositions areformulated as microemulsions said compositions are macroscopicallytransparent in the absence of opacifiers and dyes. In centrifugationexamination, it was observed that said microemulsions herein showed nophase separation after 15 minutes at 6000 rpm. Under microscopicexamination, said microemulsions appeared as a dispersion of droplets ina matrix. We have observed that the particles had a size which istypically around or below 3 micron diameter.

The bleaching compositions of the present invention, especially thoseformulated in the form of emulsions or microemulsions are chemicallystable. By "chemically stable" it is meant herein that the compositionsof the present invention comprising a peroxygen bleach do not undergomore than 10% available oxygen loss at 50° C. in 2 weeks. Theconcentration of available oxygen can be measured by chemical titrationmethods known in the art, such as the iodimetric method, thepermanganometric method and the cerimetric method. Said methods and thecriteria for the choice of the appropriate method are described forexample in "Hydrogen Peroxide", W. C. Schumb, C. N. Satterfield and R.L. Wentworth, Reinhold Publishing Corporation, New York, 1955 and"Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970.Alternatively, the stability of said compositions may also be evaluatedby a bulging test method.

Accordingly, said bleaching compositions of the present invention may bepackaged in a given deformable container/bottle without compromising thestability of said container/bottle comprising it upon standing, for longperiods of time.

Suitable chelating agents to be used herein include chelating agentsselected from the group of phosphonate chelating agents, aminocarboxylate chelating agents, polyfunctionally-substituted aromaticchelating agents, and further chelating agents like glycine, salicylicacid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof.Chelating agents when used, are typically present herein in amountsranging from 0.001% to 5% by weight of the total composition andpreferably from 0.05% to 2% by weight.

Suitable phosphonate chelating agents to be used herein may includeethydronic acid as well as amino phosphonate compounds, including aminoalkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxydiphosphonates, nitrilo trimethylene phosphonates, ethylene diaminetetra methylene phosphonates, and diethylene triamine penta methylenephosphonates. The phosphonate compounds may be present either in theiracid form or as salts of different cations on some or all of their acidfunctionalities. Preferred phosphonate chelating agents to be usedherein are diethylene triamine penta methylene phosphonates. Suchphosphonate chelating agents are commercially available from Monsantounder the trade name DEQUEST®.

The most preferred phosphonate chelating agent to be used herein isaminotri(methylene phosphonic acid), herein referred to as ATMP. Indeed,it has been found that the addition of ATMP, i.e. the compound offormula: ##STR2## in a liquid composition of the present inventionconsiderably reduces the damage otherwise associated with thepretreatment of fabrics with peroxygen bleach-containing compositions,especially those fabrics which contain metal ions, such as copper, iron,chromium, and manganese.

Polyfunctionally-substituted aromatic chelating agents may also beuseful in the compositions herein. See U.S. Pat. No. 3,812,044, issuedMay 21, 1974, to Connor et al. Preferred compounds of this type in acidform are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine N,N'-disuccinic acid, or alkali metal, or alkaline earth,ammonium or substitutes ammonium salts thereof or mixtures thereof.Ethyienediamine N,N'-disuccinic acids, especially the (S,S) isomer havebeen extensively described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, toHartman and Perkins. Ethylenediamine N,N'-disuccinic acids is, forinstance, commercially available under the tradename ssEDDS® from PalmerResearch Laboratories.

Suitable amino carboxylates to be used herein include ethylene diaminetetra acetates, diethylene triamine pentaacetates, diethylene triaminepentaacetate (DTPA),N-hydroxyethylethylenediamine triacetates,nitrilotriacetates, ethylenediamine tetrapropionates,triethylenetetraaminehexaacetates, ethanol-diglycines, propylene diaminetetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both intheir acid form, or in their alkali metal, ammonium, and substitutedammonium salt forms. Particularly suitable amino carboxylates to be usedherein are diethylene triamine penta acetic acid, propylene diaminetetracetic acid (PDTA) which is, for instance, commercially availablefrom BASF under the trade name Trilon FS® and methyl glycine di-aceticacid (MGDA).

Another preferred chelating agent for use herein is of the formula:##STR3## wherein R₁, R₂, R₃, and R₄ are independently selected from thegroup consisting of --H, alkyl, alkoxy, aryl, aryloxy, --Cl, --Br,--NO₂, --C(O)R', and --SO₂ R"; wherein R' is selected from the groupconsisting of --H, --OH, alkyl, alkoxy, aryl, and aryloxy; R" isselected from the group consisting of alkyl, alkoxy, aryl, and aryloxy;and R₅, R₆, R₇, and R₈ are independently selected from the groupconsisting of --H and alkyl.

Particularly preferred chelating agents to be used herein are ATMP,diethylene triamine methylene phosphonate, ethylene N,N'-disuccinicacid, diethylene triamine pantaacetate, glycine, salicylic acid,aspartic acid, glutamic acid, malonic acid or mixtures thereof andhighly preferred is ATMP.

Suitable radical scavengers for use herein include the well-knownsubstituted mono and dihydroxy benzenes and their analogs, alkyl andaryl carboxylates and mixtures thereof. Preferred such radicalscavengers for use herein include di-tert-butyl hydroxy toluene (BHT),hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone,tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butylcatechol, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, n-propyl-gallate or mixtures thereof and highly preferred isdi-tert-butyl hydroxy toluene. Radical scavengers when used, aretypically present herein in amounts ranging from 0.001% to 2% by weightof the total composition and preferably from 0.001% to 0.5% by weight.

The presence of chelating agents, especially ATMP, and/or radicalscavengers contributes to the safety profile of the compositions of thepresent invention suitable for pretreating a soiled colored fabric uponprolonged contact times before washing said fabric.

The compositions according to the present invention may further comprisea soil suspending polyamine polymer or mixtures thereof, as optionalingredient. Any soil suspending polyamine polymer known to those skilledin the art may also be used herein. Particularly suitable polyaminepolymers for use herein are polyalkoxylated polyamines. Such materialscan conveniently be represented as molecules of the empirical structureswith repeating units: ##STR4## wherein R is a hydrocarbyl group, usuallyof 2-6 carbon atoms; R¹ may be a C₁ -C₂₀ hydrocarbon; the alkoxy groupsare ethoxy, propoxy, and the like, and y is 2-30, most preferably from10-20; n is an integer of at least 2, preferably from 2-20, mostpreferably 3-5; and X⁻ is an anion such as halide or methylsulfate,resulting from the quaternization reaction.

The most highly preferred polyamines for use herein are the so-calledethoxylated polyethylene amines, i.e., the polymerized reaction productof ethylene oxide with ethyleneimine, having the general formula:##STR5## when y=2-30. Particularly preferred for use herein is anethoxylated polyethylene amine, in particular ethoxylatedtetraethylenepentamine, and quaternized ethoxylated hexamethylenediamine.

It has surprisingly been found that said soil suspending polyaminepolymers contribute to the benefits of the present invention, i.e., thatwhen added on top of said solvent system in a liquid compositioncomprising a peroxygen bleach, they further improve the stain removalperformance of said composition, especially under laundry pretreatmentconditions. Indeed, they allow to improve the stain removal performanceon a variety of stains including greasy stains, enzymatic stains,clay/mud stains as well as on bleachable stains.

Typically, the compositions comprise up to 10% by weight of the totalcomposition of such a soil suspending polyamine polymer or mixturesthereof, preferably from 0.1% to 5% and more preferably from 0.3% to 2%.

The compositions herein may also comprise other polymeric soil releaseagents known to those skilled in the art. Such polymeric soil releaseagents are characterised by having both hydrophilic segments, tohydrophilize the surface of hydrophobic fibres, such as polyester andnylon, and hydrophobic segments, to deposit upon hydrophobic fibres andremain adhered thereto through completion of washing and rinsing cyclesand, thus, serve as an anchor for the hydrophilic segments. This canenable stains occurring subsequent to treatment with the soil releaseagent to be more easily cleaned in later washing procedures.

The polymeric soil release agents useful herein especially include thosesoil release agents having: (a) one or more nonionic hydrophilecomponents consisting essentially of (i) polyoxyethylene segments with adegree of polymerization of at least 2, or (ii) oxypropylene orpolyoxypropylene segments with a degree of polymerization of from 2 to10, wherein said hydrophile segment does not encompass any oxypropyleneunit unless it is bonded to adjacent moieties at each end by etherlinkages, or (iii) a mixture of oxyalkylene units comprising oxyethyleneand from 1 to about 30 oxypropylene units wherein said mixture containsa sufficient amount of oxyethylene units such that the hydrophilecomponent has hydrophilicity great enough to increase the hydrophilicityof conventional polyester synthetic fiber surfaces upon deposit of thesoil release agent on such surface, said hydrophile segments preferablycomprising at least about 25% oxyethylene units and more preferably,especially for such components having about 20 to 30 oxypropylene units,at least about 50% oxyethylene units; or (b) one or more hydrophobecomponents comprising (i) C₃ oxyalkylene terephthalate segments,wherein, if said hydrophobe components also comprise oxyethyleneterephthalate, the ratio of oxyethylene terephthalate:C₃ oxyalkyleneterephthalate units is about 2:1 or lower, (ii) C₄ -C₆ alkylene or oxyC₄ -C₆ alkylene segments, or mixtures therein, (iii) poly (vinyl ester)segments, preferably polyvinyl acetate), having a degree ofpolymerization of at least 2, or (iv) C₁ -C₄ alkyl ether or C₄hydroxyalkyl ether substituents, or mixtures therein, wherein saidsubstituents are present in the form of C₁ -C₄ alkyl ether or C₄hydroxyalky ether cellulose derivatives, or mixtures therein, and suchcellulose derivatives are amphiphilic, whereby they have a sufficientlevel of C₁ -C₄ alkyl ether and/or C₄ hydroxyalkyl ether units todeposit upon conventional polyester synthetic fiber surfaces and retaina sufficient level of hydroxyls, once adhered to such conventionalsynthetic fiber surface, to increase fiber surface hydrophilicity, or acombination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from about 1 to about 200, although higher levels canbe used, preferably from 3 to about 150, more preferably from 6 to about100. Suitable oxy C₄ -C₆ alkylene hydrophobe segments include, but arenot limited to, end-caps of polymeric soil release agents such as MO₃S(CH₂)_(n) OCH₂ CH₂ O--, where M is sodium and n is an integer from 4-6,as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 toGosselink.

Polymeric soil release agents useful in the present invention alsoinclude cellulosic derivatives such as hydroxyether cellulosic polymers,co-polymeric blocks of ethylene terephthalate or propylene terephthalatewith polyethylene oxide or polypropylene oxide terephthalate, and thelike. Such agents are commercially available and include hydroxyethersof cellulose such as METHOCEL (Dow). Cellulosic soil release agents foruse herein also include those selected from the group consisting of C₁-C₄ alkyl and C₄ hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093,issued Dec. 28, 1976 to Nicol, et al.

Soil release agents characterised by poly(vinyl ester) hydrophobesegments include graft co-polymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. See EuropeanPatent Application 0 20 219 048, published Apr. 22, 1987 by Kud, et al.Commercially available soil release agents of this kind include theSOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (WestGermany).

One type of preferred soil release agent is a co-polymer having randomblocks of ethylene terephthalate and polyethylene oxide (PEO)terephthalate. The molecular weight of this polymeric soil release agentis in the range of from about 25,000 to about 55,000. See U.S. Pat. No.3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 toBasadur issued Jul. 8, 1975.

Another preferred polymeric soil release agent is a polyester withrepeat units of ethylene terephthalate units which contains 10-15% byweight of ethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000. Examples of this polymerinclude the commercially available material ZELCON 5126 (from Dupont)and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct.27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated productof a substantially linear ester oligomer comprised of an oligomericester backbone of terephthaloyl and oxyalkyleneoxy repeat units andterminal moieties covalently attached to the backbone. These soilrelease agents are fully described in U.S. Pat. No. 4,968,451, issuedNov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitablepolymeric soil release agents include the terephthalate polyesters ofU.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, theanionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issuedJan. 26, 1988 to Gosselink, and the block polyester oligomeric compoundsof U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil releaseagents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado etal, which discloses anionic, especially sulfoaroyl, end-cappedterephthalate esters.

Still another preferred soil release agent is an oligomer with repeatunits of terephthaloyl units, sulfoisoterephthaloyl units,oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form thebackbone of the oligomer and are preferably terminated with modifiedisethionate end-caps. A particularly preferred soil release agent ofthis type comprises about one sulfoisophthaloyl unit, 5 terephthaloylunits, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of fromabout 1.7 to about 1.8, and two end-cap units of sodium2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent alsocomprises from about 0.5% to about 20%, by weight of the oligomer, of acrystalline-reducing stabilizer, preferably selected from the groupconsisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, andmixtures thereof. See U.S. Pat. No. 5,41 5,807, issued May 16, 1995, toGosselink et al.

If utilised, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

The compositions of the present invention may also include one or morematerials effective for inhibiting the transfer of dyes from one dyedsurface to another during the cleaning process. Generally, such dyetransfer inhibiting agents include polyvinyl pyrrolidone polymers,polyamine N-oxide polymers, co-polymers of N-vinylpyrrolidone andN-vinylimidazole, manganese phthalocyanine, peroxidases, and mixturesthereof If used, these agents typically comprise from about 0.01% toabout 10% by weight of the composition, preferably from about 0.01% toabout 5%, and more preferably from about 0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R--A_(x)--P; wherein P is a polymerizable unit to which an N--O group can beattached or the N--O group can form part of the polymerizable unit orthe N--O group can be attached to both units; A is one of the followingstructures: --NC(O)--, --C(O)O--, --S--, --O--, --N=; x is 0 or 1; and Ris aliphatic, ethoxylated aliphatics, aromatics, heterocyclic oralicyclic groups or any combination thereof to which the nitrogen of theN--O group can be attached or the N--O group is part of these groups.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine andderivatives thereof.

The N--O group can be represented by the following general structures:##STR6## wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic oralicyclic groups or combinations thereof; x, y and z are 0 or 1; and thenitrogen of the N--O group can be attached or form part of any of theaforementioned groups.

The amine oxide unit of the polyamine N-oxides has a pKa<10, preferablypKa<7, more preferred pKa<6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block co-polymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate co-polymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as "PVNO". The most preferred polyamine N-oxide useful inthe detergent compositions herein is poly(4-vinylpyridine-N-oxide) whichas an average molecular weight of about 50,000 and an amine to amineN-oxide ratio of about 1:4.

Co-polymers of N-vinylpyrrolidone and N-vinylimidazole polymers(referred to as a class as "PVPVI") are also preferred for use herein.Preferably the PVPVI has an average molecular weight range from 5,000 to1,000,000, more preferably from 5,000 to 200,000, and most preferablyfrom 10,000 to 20,000. (The average molecular weight range is determinedby light scattering as described in Barth, et al., Chemical Analysis,Vol 113. "Modern Methods of Polymer Characterization", the disclosuresof which are incorporated herein by reference.) The PVPVI co-polymerstypically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidonefrom 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferablyfrom 0.6:1 to 0.4:1. These co-polymers can be either linear or branched.

The present invention compositions may also employ apolyvinylpyrrolidone ("PVP") having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol ("PEG")having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

If high sudsing is desired, suds boosters such as C₁₀ -C₁₆ alkanolamidescan be incorporated into the compositions, typically at 1%-10% levels.The C₁₀ -C₁₄ monoethanol and diethanol amides illustrate a typical classof such suds boosters. Use of such suds boosters with high sudsingadjunct surfactants such as the amine oxides, betaines and sultainesnoted above is also advantageous. If desired, soluble magnesium saltssuch as MgCl₂, MgSO₄, and the like, can be added at levels of, forexample, 0.1%-2%, to provide additional suds and to enhance greaseremoval performance.

Any optical brighteners, fluorescent whitening agents or otherbrightening or whitening agents known in the art can be incorporated inthe instant compositions when they are designed for fabric treatment orlaundering, at levels typically from about 0.05% to about 1.2%, byweight, of the detergent compositions herein. Commercial opticalbrighteners which may be useful in the present invention can beclassified into subgroups, which include, but are not necessarilylimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacids, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and6-membered-ring heterocyclic brighteners, this list being illustrativeand non-limiting. Examples of such brighteners are disclosed in "TheProduction and Application of Fluorescent Brightening Agents", M.Zahradnik, Published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, available fromHilton-Davis, located in Italy; the2-(4-styryl-phenyl)-2H-naphthol[1,2-d]triazoles;4,4'-bis-(1,2,3-triazol-2-yl)-stil-benes; 4,4'-bis(styryl)bisphenyls;and the aminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene;2,5-bis(benzoxazol-2-yl)thiophene; 2-styrylnapth-[1,2-d]oxazole; and2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972, to Hamilton. Anionic brighteners aretypically preferred herein.

If desired, compositions herein may additionally incorporate a catalystor accelerator to further improve bleaching or soil removal. Anysuitable bleach catalyst can be used. For detergent compositions used ata total level of from about 1,000 to about 5,000 ppm in water, thecomposition will typically deliver a concentration of from about 0.1 ppmto about 700 ppm, more preferably from about 1 ppm to about 50 ppm, orless, of the catalyst species in the wash liquor.

Bleach catalysts may also be used herein. Typical bleach catalystscomprise a transition-metal complex, for example one wherein the metalco-ordinating ligands are quite resistant to labilization and which doesnot deposit metal oxides or hydroxides to any appreciable extent underthe typically alkaline conditions of washing. Such catalysts includemanganese-based catalysts disclosed in U.S. Pat. Nos. 5,246,621,5,244,594; 5,194,416; 5,114,606; and EP Nos. 549,271 A1, 549,272 A1,544,440 A2, and 544,490 A1; preferred examples of these catalystsinclude Mn^(IV) ₂ (μ-O)₃ (TACN)₂ --(PF₆)₂, Mn^(III) ₂ (μ-O)₁ (μ-OAc)₂(TACN)₂ (ClO₄)₂, Mn^(IV) ₄ (μ-O)₆ (TACN)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄--(μ-O)₁ (μ-OAc)₂ --(TACN)₂ --(ClO₄)₃, Mn^(IV-) (TACN)--(OCH₃)₃ (PF₆),and mixtures thereof wherein TACN is trimethyl-1,4,7-triazacyclononaneor an equivalent macrocycle; though alternate metal-co-ordinatingligands as well as mononuclear complexes are also possible andmonometallic as well as di- and polymetallic complexes and complexes ofalternate metals such as iron or ruthenium are all within the presentscope. Other metal-based bleach catalysts include those disclosed inU.S. Pat. Nos. 4,430,243 and 5,114,611. The use of manganese withvarious complex ligands to enhance bleaching is also reported in thefollowing U.S. Pat. Nos.: 4,728,455; 5,284,944; 5,246,612; 5,256,779;5,280,117; 5,274,147; 5,153,161; and 5,227,084.

Transition metals may be precomplexed or complexed in-situ with suitabledonor ligands selected in function of the choice of metal, its oxidationstate and the denticity of the ligands. Other complexes which may beincluded herein are those of U.S. application Ser. No. 08/210,186, filedMar. 17, 1994.

Depending on the end-use envisioned, the compositions herein can bepackaged in a variety of containers including conventional bottles,bottles equipped with roll-on, sponge, brusher or sprayers, or sprayers.

Although the preferred application of the liquid compositions describedherein is laundry application, as a laundry detergent or as a laundryadditive and especially as a pretreater such compositions may also beused to clean hard-surfaces.

The invention is further illustrated by the following examples.

EXAMPLES Example 1

A liquid composition is prepared which comprises:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        Hydrogen peroxide      6%                                                     ATC                    2%                                                     Benzyl alcohol (HI = 16)                                                                             2%                                                     Pinene (HI = 0)        1%                                                     Ethoxyethoxy ethanol (HI = 37)                                                                       4%                                                     Dobanol ® 23.3     8.6%                                                   Dobanol ® 45.7     6.4%                                                   C12 Alkyl Sulfate      2%                                                     Water and minors       up to 100%                                             ______________________________________                                         pH = 4, trimmed with Sulphuric acid                                      

In a pretreatment mode, this composition is applied neat on the stainedportion of a fabric and left to act thereon for 5 minutes. Then thefabric is washed with a conventional detergent and rinsed. Excellentstain removal is obtained therewith on various stains including greasystains, enzymatic stains, clay stains and bleachable stains.

Example 2

A liquid composition is prepared which comprises:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        Hydrogen peroxide      4.0%                                                   ATC                    3.5%                                                   Benzyl alcohol (HI = 16)                                                                             2%                                                     Methoxy Propanol (HI = 37)                                                                           5%                                                     Limonene (HI = 0)      1%                                                     Dobanol ® 23.3     8.6%                                                   Dobanol ® 45.7     6.4%                                                   C12 Alkyl Sulfate      2%                                                     Water and minors       up to 100%                                             ______________________________________                                         pH = 4, trimmed with Sulphuric acid                                      

In a pretreatment mode, this composition is applied neat on the stainedportion of a fabric and left to act thereon for 5 minutes. Then thefabric is washed with a conventional detergent and rinsed. Excellentstain removal is obtained therewith on various stains including greasystains, enzymatic stains, clay stains and bleachable stains.

Example 3

The following liquid composition is prepared:

    ______________________________________                                                              (weight %)                                              ______________________________________                                        Hydrogen peroxide       6.0%                                                  ATC                     3.5%                                                  Benzyl alcohol (HI = 16)                                                                              1%                                                    Pinene (HI = 0)         0.5%                                                  Propoxy propanol (HI = 28)                                                                            5%                                                    Dobanol ® 45.7      6.0%                                                  Dobanol ® 23.6,5    6.0%                                                  C25-AE2.5-S (ethoxylated alkyl sulfate)                                                               12.0%                                                 Water and minors        up to 100%                                            ______________________________________                                         pH = 4, trimmed with Sulphuric acid                                      

In a bleaching-through-the-wash mode, this composition is contacted withan aqueous bath formed by dissolution of a conventional detergent inwater. Fabrics are then contacted with the aqueous bath comprising theliquid detergent, and the fabrics are rinsed. This composition can alsobe used in a pretreatment mode, where it is poured neat on the stains onthe fabrics, and left to act for 5 minutes, and the fabrics are washed.Excellent stain removal is obtained on various stains including greasystains, enzymatic stains, clay stains and bleachable stains.

Example 4

The following liquid composition is prepared:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        tert-Butyl Hydroperoxide                                                                             5%                                                     EthoxyEthoxyEthanol (HI = 37)                                                                        8%                                                     Limonene (HI = 0)      2%                                                     Dobanol ® 91.10    1.6%                                                   Dobanol ® 23.3     1.5%                                                   C10 Alkyl sulphate     1.7%                                                   Isofol 12 ®        0.5%                                                   Water and minors       up to 100%                                             ______________________________________                                         pH = 4, trimmed with Sulphuric acid                                      

This composition can be used in a pretreatment mode, or in ableaching-through-the-wash mode, as described in previous examples. Itcan also be used in a soaking mode, where 100 ml of the liquidcompositions are diluted in 10 liters of water. The fabrics are thencontacted with this aqueous bath containing the composition, and left tosoak therein for a period of time of 24 hours. The fabrics areeventually rinsed. Excellent stain removal is obtained therewith onvarious stains including greasy stains, enzymatic stains, clay stainsand bleachable stains.

Example 5

The following liquid composition is prepared:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        tert-Butyl Hydroperoxide                                                                             5%                                                     EthoxyEthoxyEthanol (HI = 37)                                                                        8%                                                     Pimene (HI = 0)        2%                                                     Dobanol ® 91.10    1.6%                                                   Dobanol ® 23.3     1.5%                                                   C10 Alkyl sulphate     1.7%                                                   Isofol 12 ®        0.5%                                                   Water and minors       up to 100%                                             ______________________________________                                         pH = 4, trimmed with Sulphuric acid                                      

This composition can be used in a pretreatment mode, or in ableaching-through-the-wash mode, as described in previous examples. Itcan also be used in a soaking mode, where 100 ml of the liquidcompositions are diluted in 10 liters of water. The fabrics are thencontacted with this aqueous bath containing the composition, and left tosoak therein for a period of time of 24 hours. The fabrics areeventually rinsed. Excellent stain removal is obtained therewith onvarious stains including greasy stains, enzymatic stains, clay stainsand bleachable stains.

Example 6

The following liquid composition is prepared:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        H2O2                   7%                                                     EthoxyEthoxyEthanol (HI = 37)                                                                        1%                                                     Limonene (HI = 0)      0.2%                                                   Dobanol ® 91.10    1.6%                                                   Dobanol ® 23.3     1.5%                                                   C10 AS                 1.7%                                                   Isofol 12 ®        0.5%                                                   Water and minors       up to 100%                                             ______________________________________                                         pH = 4, trimmed with Sulphuric acid                                      

This composition can be used in a pretreatment mode, or in ableaching-through-the-wash mode, as described in examples 1 and 2. Itcan also be used in a soaking mode, where 100 ml of the liquidcompositions are diluted in 10 liters of water. The fabrics are thencontacted with this aqueous bath containing the composition, and left tosoak therein for a period of time of 24 hours. The fabrics areeventually rinsed. Excellent stain removal is obtained therewith onvarious stains including greasy stains, enzymatic stains, clay stainsand bleachable stains.

Example 7

A liquid detergent composition is prepared as follows:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        Cumyl Hydroperoxide    10%                                                    Ethoxyethoxy ethanol (HI = 37)                                                                       4.0%                                                   Benzyl alcohol (HI = 16)                                                                             1.5%                                                   Dobanol ® 23.3     8.6%                                                   Dobanol ® 45.7     6.4%                                                   C12 AS                 2%                                                     Water and minors       up to 100%                                             ______________________________________                                         pH = 6, trimmed with Sulphuric acid                                      

This composition is used in a pretreatment mode, as described in theexamples above. Excellent stain removal is obtained therewith on variousstains including greasy stains, enzymatic stains, clay stains andbleachable stains.

Example 8

The following liquid composition is made:

    ______________________________________                                                               (weight %)                                             ______________________________________                                        2,5-dimethyl-hexane-2,5-dihydroperoxide                                                                5%                                                   Propoxy propanol (HI = 28)                                                                             8%                                                   Pinene (HI = 0)          1.0%                                                 Dobanol ® 23.3       8.6%                                                 Dobanol ® 45.7       6.4%                                                 C25-2.5EO-S              2%                                                   Water and minors         up to 100%                                           ______________________________________                                         pH = 5, trimmed with Sulphuric acid                                      

This composition is used in a pretreatment mode as described in theprevious examples. Excellent stain removal is obtained therewith onvarious stains including greasy stains, enzymatic stains, clay stainsand bleachable stains.

Example 9

The following liquid composition is made:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        Dilauroyl peroxide     2.0%                                                   Methoxy propanol (HI = 37)                                                                           4.0%                                                   Benzyl alcohol (HI = 16)                                                                             1.0%                                                   Dobanol ® 23.3     8.6%                                                   Dobanol ® 45.7     6.4%                                                   C12 alkyl suphate      1.0%                                                   Water and minors       up to 100%                                             ______________________________________                                         pH = 5, trimmed with Sulphuric acid                                      

This composition is used in a pretreatment mode as described in theprevious examples. Excellent stain removal is obtained therewith onvarious stains including greasy stains, enzymatic stains, clay stainsand bleachable stains.

Example 10

The following liquid composition is made:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        Dilauroyl peroxide     0.5%                                                   Hydrogen peroxide      4.0%                                                   ATC                    2.0%                                                   Methoxy propanol (HI = 37)                                                                           5.0%                                                   Benzyl alcohol (HI = 16)                                                                             2.0%                                                   Limonene (HI = 0)      0.5%                                                   Dobanol ® 23.3     8.6%                                                   Dobanol ® 45.7     6.4%                                                   C25-2.5EO-S            2%                                                     Water and minors       up to 100%                                             ______________________________________                                         pH = 5, trimmed with Sulphuric acid                                      

In the previous examples ATC stands for acetyl triethyl citrate.

This composition is used in a pretreatment mode as described in theprevious examples. Excellent stain removal is obtained therewith onvarious stains including greasy stains, enzymatic stains, clay stainsand bleachable stains.

Example 11

The following liquid composition is prepared:

    ______________________________________                                                             (weight %)                                               ______________________________________                                        Didecanoyl peroxide    0.5%                                                   Hydrogen peroxide      7.0%                                                   Ethoxy propanol (HI = 32)                                                                            1.0%                                                   Limonene (HI = 0)      0.2%                                                   Dobanol ® 91.10    1.5%                                                   C10 Alkyl sulphate     1.7%                                                   Water and minors       up to 100%                                             ______________________________________                                         pH = 4, trimmed with Sulphuric acid                                      

This composition can be used in a pretreatment mode, or in ableaching-through-the-wash mode, as described in previous examples.Excellent stain removal is obtained therewith on various stainsincluding greasy stains, enzymatic stains, clay stains and bleachablestains.

What is claimed is:
 1. A process of bleaching a fabric with an aqueous liquid composition comprising a peroxygen bleach and a solvent system comprising a hydrophilic organic solvent having a hydrophilic index of more than 18, and a hydrophobic organic solvent having a hydrophilic index of less than 18, wherein said composition has a pH of from 1 to 6, and wherein the hydrophilic index is defined by the equation ##EQU6## said process comprising the steps of applying said composition in its neat form onto said fabric, before rinsing or washing, then rinsing said fabric.
 2. A process according to claim 1, wherein said neat composition is allowed to remain in contact with said fabric for a period of time ranging from 1 minute to 1 hour.
 3. A process according to claim 2, wherein said neat composition is allowed to remain in contact with said fabric for a period of time ranging from 1 minute to 30 minutes.
 4. A process of bleaching fabrics which includes the steps of diluting in an aqueous bath an aqueous liquid composition in its neat form, said composition comprising a peroxygen bleach one or more other ingredients selected from the group consisting of radical scavengers, soil suspending polyamine polymers, other polymeric soil release agents, dye transfer inhibiting agents, suds boosting agents, bleach catalysts and mixtures thereof, and a solvent system comprising a hydrophilic organic solvent having a hydrophilic index of more than 18, and a hydrophobic organic solvent having a hydrophilic index of less than 18, wherein said composition has a pH of from 1 to 6, and wherein the hydrophilic index is defined by the equation ##EQU7## contacting said fabrics with said aqueous bath comprising said liquid composition, and subsequently rinsing, or washing then rinsing said fabrics.
 5. A process according to claim 4, wherein the fabrics are left to soak in said aqueous bath comprising said liquid composition for a period of time ranging from 30 minutes to 48 hours.
 6. A process according to claim 5, wherein the fabrics are left to soak in said aqueous bath comprising said liquid composition for a period of time ranging from 1 hour to 24 hours.
 7. A process according to claim 6, wherein said aqueous bath is formed by dissolving or dispersing a conventional laundry detergent in water.
 8. A process according to claim 1, wherein said neat composition comprises from 0.01% to 20% by weight of the total composition of a peroxygen bleach or mixtures thereof.
 9. A process according to claim 8, wherein said neat composition comprises from 1% to 10% by weight of the total composition of a peroxygen bleach or mixtures thereof.
 10. A process according to claim 1 wherein said hydrophilic solvent is an alkoxylated aliphatic or aromatic alcohol having a hydrophilic index of more than 18, an aliphatic or aromatic alcohol having a hydrophilic index of more than 18, glycol or alkoxylated glycol having a hydrophilic index of more than 18, or mixtures thereof.
 11. A process according to claim 1 wherein said hydrophilic solvent is ethanol, propanol, methoxy propanol, ethoxy propanol, propoxy propanol, buthoxy propanol, propanediol, ethoxy-ethoxy-ethanol or mixtures thereof.
 12. A process according to claim 1 wherein said hydrophobic solvent is a paraffin, a terpene or a terpene derivative having a hydrophilic index of less than 18, an alkoxylated aliphatic or aromatic alcohol having a hydrophilic index of less than 18, an aliphatic or aromatic alcohol having a hydrophilic index of less than 18, glycol or alkoxylated glycol having a hydrophilic index of less than 18, or mixtures thereof.
 13. A process according to claim 1 wherein said hydrophobic solvent is d-limonene, dipentene, alpha-pinene, beta-pinene, octane, benzyl alcohol or mixtures thereof.
 14. A process according to claim 1 wherein said composition comprises from 0.1% to 5% by weight of the total composition of a hydrophobic solvent or mixtures thereof.
 15. A process according to claim 1 wherein said composition comprises from 0.5% to 15% by weight of the total composition of a hydrophilic solvent or mixtures thereof.
 16. A process according to claim 1 wherein said composition comprises from 0.2% to 2% by weight of the total composition of a hydrophobic solvent or mixtures thereof.
 17. A process according to claim 1 wherein said composition comprises from 1% to 10% by weight of the total composition of a hydrophilic solvent or mixtures thereof.
 18. A process according to claim 1 wherein said composition has a pH of from 2 to
 6. 19. An aqueous liquid composition suitable for bleaching fabrics, comprising a peroxygen bleach, one or more other ingredients selected from the group consisting of radical scavengers, soil suspending polyamine polymers, other polymeric soil release agents, dye transfer inhibiting agents, suds boosting agents, bleach catalysts and mixtures thereof, and a solvent system comprising from 0.05% to 20% by weight of the total composition of a hydrophilic organic solvent having a hydrophilic index of more than 18, and from 0.05% to 10% by weight of the total composition of a hydrophobic organic solvent having a hydrophilic index of less than 18, wherein said composition has a pH of from 1 to 6, and wherein the hydrophilic index is defined by the equation ##EQU8##20.
 20. A composition according to claim 19 wherein said composition comprises from 0.01% to 20% by weight of the total composition of a peroxygen bleach or mixtures thereof.
 21. A composition according to claim 19 wherein said neat composition comprises from 1% to 10% by weight of the total composition of a peroxygen bleach or mixtures thereof.
 22. A composition according to claim 19 wherein said hydrophilic solvent is an alkoxylated aliphatic or aromatic alcohol having a hydrophilic index of more than 18, an aliphatic or aromatic alcohol having a hydrophilic index of more than 18, glycol or alkoxylated glycol having a hydrophilic index of more than 18, or mixtures thereof.
 23. A composition according to claim 19 wherein said hydrophilic solvent is ethanol, propanol, methoxy propanol, ethoxy propanol, propoxy propanol, buthoxy propanol, propanediol, ethoxy-ethoxy-ethanol or mixtures thereof.
 24. A composition according to claim 19 wherein said hydrophobic solvent is a paraffin, a terpene or a terpene derivative having a hydrophilic index of less than 18, an alkoxylated aliphatic or aromatic alcohol having a hydrophilic index of less than 18, an aliphatic or aromatic alcohol having a hydrophilic index of less than 18, glycol or alkoxylated glycol having a hydrophilic index of less than 18, or mixtures thereof.
 25. A composition according to claim 19 wherein said hydrophobic solvent is d-limonene, dipentene, alpha-pinene, beta-pinene, octane, benzyl alcohol or mixtures thereof.
 26. A composition according to claim 19 wherein said composition comprises from 0.1% to 5% by weight of the total composition of a hydrophobic solvent or mixtures thereof.
 27. A composition according to claim 19 wherein said composition comprises from 0.5% to 15% by weight of the total composition of a hydrophilic solvent or mixtures thereof.
 28. A composition according to claim 19 wherein said composition comprises from 0.2% to 2% by weight of the total composition of a hydrophobic solvent or mixtures thereof.
 29. A composition according to claim 19 wherein said composition comprises from 1% to 10% by weight of the total composition of a hydrophilic solvent or mixtures thereof.
 30. A composition according to claim 19 wherein said composition has a pH of from 2 to
 6. 31. A process according to claim 1 wherein said peroxygen bleach is selected from the group consisting of percarbonate, persilicate, persulphate, perborate, peroxyacids, alkyl hydroperoxides, peroxides, aliphatic diacyl peroxides and mixtures thereof.
 32. A process according to claim 1 wherein the composition further comprises a hydrophobic nonionic surfactant having an HLB below 16 and mixtures thereof.
 33. A composition according to claim 19 wherein said peroxygen bleach is selected from the group consisting of percarbonate, persilicate, persulphate, perborate, peroxyacids, alkyl hydroperoxides, peroxides, aliphatic diacyl peroxides and mixtures thereof.
 34. A composition according to claim 19 wherein the composition further comprises a hydrophobic nonionic surfactant having an HLB below 16 and mixtures thereof. 